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(338f) Modeling the Hydrolytic Degradation and Distribution of Polymer Species In Biopolymers

Huang, H., University of Minnesota
Tschirner, U., University of Minnesota
Schroeder, B., University of Minnesota
Al-dajani, W., University of Minnesota

Modeling the
hydrolytic degradation and distribution of polymer species in biopolymers

Justin Kaffenberger, Huajiang Huang, Ulrike Tschirner, Ben
Schroeder, Waleed Al-dajani, and Shri Ramaswamy

Department of Bioproducts and Biosystems Engineering,
University of Minnesota, St. Paul, MN 55108


The US Department of Energy in its Plant/Crop-Based
Renewable Resources Report 2020 has put forth an initiative to have 10 percent of
chemical feedstock coming from plant-based renewable sources by 2020 and a
further increase to 50 percent by 2050.[1]  Meeting these targets will require production
of current chemical feedstocks from renewable sources, such as the dehydration
of plant-based ethanol to produce ethylene. 
It will also require the development of alternative feedstocks that can
supplant the petroleum-based ones that currently predominate.  One example of a chemical feedstock of
increasing importance is lactic acid. 

Lactic acid is a metabolite formed during glucose
fermentation by many organisms.  Due to
its versatility, lactic acid has the potential to be a major renewable chemical
feedstock.  It can be esterified to form
lactate esters, reduced to propylene glycol, or dehydrated to acrylic acid.[2]  It can also be homopolymerized to form
polylactic acid (PLA) via condensation reaction.  The resulting polymer exhibits mechanical
properties similar to many petroleum-based polymers, including polyethylene
teraphthalate, polyethylene, and polystyrene. 

The degradability of PLA is critical to its current
commercial success.  In disposable food
packaging and service ware, the degradability and bio-absorptivity of the
degradation product of PLA makes it marketable as a green and environmentally-friendly
product.  In biomedical applications, the
degradability and biocompatibility of PLA are essential.  As PLA's ability to degrade is a major factor
in its application functionality, understanding the fundamentals of this
process is critical to all stages of PLA manufacture and end-use application. 

To this end, a mathematical model has been developed that
predicts the time dependent change in the average molecular weight of
polylactic acid (PLA) of varying crystallinity as it hydrolytically degrades at
a given temperature. This model includes three possible hydrolysis reaction
routes: random chain scission, end scission (monomer removal from the acid end
group, and monomer removal from the alcohol end group).  Apparent rate constants for these reaction
pathways were determined from experimental data.  The resulting values suggest that,
independent of the crystallinity of the starting PLA, acid end groups are
hydrolyzed more rapidly than either alcohol end groups or random chain
scission.  This may help develop suitable
approaches to control the polymer properties and degradation and help develop
wider application for PLA products.